Sulfated hydroxy alkyl thio succinates



Patented Mar. 3, 1953 UNITED STATES SULFATED HYDROXYAIJKYL THIO" S UCCINATES? Edward S. Blakc',,.Lexington, Mass.,..assignor.to Monsanto Chemical Company stgLouis', Moi, a corporation of;Dela,ware

No.Drawing. Applicationilulyil8,=a1949; Serial No. 105E197;

*2 Claims (c1. zenissy:

This invention relates to new andnsefulcom-M.

posl-tionstof matters. More particularly it. relates to sulfated products of hydroxy alkyhthio sue-M cinates of the general formula MSO4-RSOH-O 0.0 R

CHZTO 0 R whereM is an; alkali. metal such as sodium :and potassium, or an ammonium or hydrocarbonsub stituted ammonium group; where R isan alkylone group; and where R and R" are. selected from the group consisting of hydrogen and hydrocarbon groups. Typical examples of hydrocarbon groups comprise alkyl, aralkyl, and aryl srounslsuch aslmethyl; ethyl;v n-propy1;..isopr0py1 n-butyl, isobutyl, tert. butyl, amyl, hexylifoctyl decyl, dodecyl, pentadecyl, octadecyl, allyl, oleyl, benzl, phenethyl, phenyl, tetrahydrofurfuryl, and the like. In the same molecule R and R" cannotboth he hydrogen, andwhere R'iandR: are

hydrocarbon groups they need not belike hydro able conditions and neutralizing the resultantproduct, e. ;g., with. alkali metal .hydroxides;., The hydroxy'. alkyl .thio .succinates-p are;.prepared by the addition of a hydroxyl substituted aliphatic mercaptan, such as mercapto ethanol, mercapto propanol, mercapto butanol, and the like, to maleic acid and its esters as described in co-pending application Serial No. 742,468 filed April 18, 1947, now United States Patent 2,477,327 granted July 26, 1949.

As exemplary of the preparation of the new materials the following is illustrative and in nowise is to be considered limitative thereof.

Example 1 The di-lorol ester of S-hydroxy ethyl thio succinic acid was prepared according to co-pending application Serial No. 742,468, filed April 18, 1947, by reacting substantially 48 parts by weight of di-lorol maleate, obtained by esterifying maleic acid with lorol which is a mixture of monohydric cocoanut alcohols consisting predominately of C12 alcohols, with approximately 7.8 parts by weightof mercapto ethanol ina suitablecontainer in. the ..presence of 1 approximately 3 parts by weight .of the;- catalyst sodiummethylate. Upon; s r y l a'fi e catalyst with .dilute acid; the organic, layerwwas taken up in a waterimmiscible:

solvent. dried, over anhydrous sodium?sulfate,.1and;filtered The solution iwasjwashed -until neutral,

through a bed of Attapulgus .clay. Upon removal of...the solvent approximately 54 pants by weight of. a lights-:YG-HQW oil believed-toscomprise the di- 1 lorol ester of .p-h-ydroxy. ethyl thio; sueci-nic' acid a was obtained.

26.5 parts by .weight of the. above, described hydroxyalkyhthio, succinateiwas dissolved in 60, pa -ts: bvvweis t carbon.tetracmotidesmiths solution pooled tom-5910..v Thereto was added .6

parts by weight of chlorosulfonic acid over a period ;of..1:20. to. 25..minutes;-with agitation, while keeping; the .temperature below 1030.: Agitation:

Q was .,continuedafter completion of the. acid addir.

tion- {for a shortperiod-andmhe solution wasysu sequently.neutralized-with. a ,lO percent aqueous soda ash solution. Upon distilling ofi thesolvent apQLO imateIw-a theoretical;ryieldxoi a wax lilge of the di-lorolester of fi-hydroxy ethyl thio succinic acid was obtained. 1

Example. 2

product believed to comprise the SQQlIlIII'gSHlfQJZQ-J:

a Equal molecular quantitiesofmercapto ethanol and di-oley-l maleatewere mixed in a suitable conj-jx tainer in the -presence of approximately hairs mole of sodiummethylateas a catalysth Themix--;

:thermic'lreactiontook -placen- Dilute --acid was" added to destroy the catalyst and the organic layer was taken up in a water immiscible solvent and thereafter the solution was washed neutral. The solution was then dried over anhydrous so- 40 dium sulfate and filtered through a bed of Attapulgus clay. Upon removal of the solvent substantially a theoretical yield of a light yellow oil believed to comprise the di-oleyl ester of fl-hydroxy ethyl thio succinic acid was obtained.

34.7 parts by weight of the above prepared hydroxy alkyl thio succinate was dissolved in 160 parts by weight of carbon tetrachloride. While retaining the temperature at 30-35 C., 6 parts by weight of chlorosulfonic acid was slowly added. Upon completion of the acid addition agitation was continued for a short time and thereafter the solution was neutralized with an aqueous solution of soda ash. Upon distilling off the solvent approximately a theoretical yield of a waxlike product believed to comprise the sodium sul- 3 fate of the di-oleyl ester of 5-hydroxy ethyl succinic acid was obtained.

Example 3 Replacing di-oleyl maleate in Example 2 with di-octadecyl maleate, obtained by esterifying maleic acid with octadecyl alcohol, and reacting with mercapto ethanol in the manner described results in a product believed to comprise the diocta-decyl ester of fl-hydroxy ethyl thio succinic.

acid. Upon sulf-ating according to the procedure of Example 2 and neutralizin with soda ash, a wax-like product believed to comprise the sodium sulfate of the di-octadecyl ester of fi-hydroxy ethyl thio succinic acid is obtained.

By replacing soda ash in the above examples with such acid neutralizing material as potassium carbonate, ammonium hydroxide, mono-, di-, and tri-amines, such as the methyl amines, the ethanol amines, the butyl amines, the amyl amines, the cyclo-hexyl amines, and the like, respectively, the corresponding potassium, ammonium, and hydrocarbon substituted ammonium sulfates of hydroxy alkyl thio succinates are obtained. A particularly economical and useful neutralizing agent is caustic soda.

A particularly useful group of the new chemicals are those where R and R" in the above described general formula are branched or straight chain aliphatic groups containing from to 18 carbon atoms and where M is an alkali metal such as sodium.

Other sulfating agents than chlorosulfonic acid may be employed to produce the new materials, as for example, oleum, and other temperatures may be employed than those specifical- 1y shown.

While the invention has been described with respect to several specific embodiments, it is to be understood that modification and variations thereof may be resorted to without departing from the spirit or scope of the invention.

What is claimed is:

1. As a new composition of matter a. compound of the formula where M is selected from the group consisting of alkali metals, ammonium and hydrocarbon substituted ammonium groups, where R is an alkylene group containing more than one but less than five carbon atoms, and where R and R" are selected from the group consisting of alkyl, phenalkyl and phenyl groups containing 4 not more than 18 carbon atoms and hydrogen, but where R and R" are not both hydrogen atoms.

2. As a new composition of matter a compound of the formula MSO4RSOHCO.OR

HzC0.0R"

where M is an alkali metal, where R is an alkylene group containing more than one but less than five carbon atoms, and where R and R" are alkyl groups containing not more than 18 carbon atoms.

3. As a new composition of matter a compound of the formula M-S O4"C2EASCHC0.0 R

one-00.012"

where M is an alkali metal and where R and R" are alkyl groups containing not more than 18 carbon atoms.

4. As a new composition of matter a compound of the formula M-S 0iC2H S-CHO0.OR

om-C 0. o R

where M is an alkali metal and where R and R" are alkyl groups containing from 10 to 18 carbon atoms.

5. As a new composition of matter a compound of the formula N83 O4-C2H4SCHCO.OC12H25 CHr-C O .O G12H25 -6. As a new composition of matter a compound of the formula V NaS 04C2H4S-CHC 0.001811.

CHr-C 0.0 C18H37 7. As a new composition of matter a compound of the formula NaS O4-CzH4S-CHC O.OC1sHa5 CHz00.0CiaHss EDWARD S. BLAKE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,225,673 'Werntz Dec. 24, 1940 2,477,327 Blake July 26, 1949 

1. AS A NEW COMPOSITION OF MATTER A COMPOUND OF THE FORMULA 